Fluorine-containing epoxy resin composition readily soluble in solvent

ABSTRACT

A fluorine-containing epoxy resin composition at least contains: a fluorine-containing epoxy resin composition at least containing: a component (a) in an amount of from 5 to 80 parts by weight; a component (b) in an amount of from 5 to 40 parts by weight; and a component (c) in an amount of from 5 to 80 parts by weight, wherein the component (a) comprises a polyfunctional epoxy resin having two or more epoxy groups in one molecule and not containing F and Si; the component (b) comprises an epoxy compound having a perfluoro group at a terminal; and the component (c) comprises a compound containing in one molecule two or more of one kind or two or more kinds selected from an epoxy group, an alcohol group, a carboxylic acid group, and an amine group. The fluorine-containing epoxy resin composition is suitably usable for treating a specified surface of a member or device so as to impart a liquid repellent property thereto. The resin composition is also usable as an adhesive for bonding members to each other, and as a paint when added with a coloring material diffused therein.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a fluorine-containing epoxy resincomposition which is readily soluble in commonly used organic solventsand enables formation of a high quality coating film excellent insurface properties (hardness and smoothness), liquid repellent property,and adhesion property. The present invention also relates to a processof treating a surface of an object using said resin composition so as toform a surface excellent in surface properties (hardness andsmoothness), adhesion property, and liquid repellent property on theobject.

2. Related Background Art

It has been known that liquid repellent agents commonly used are stablethermally and chemically and are excellent in weatherability, watertightness, chemical resistance, solvent resistance, mold releasability,and liquid repellent property; however, they are not necessarilysatisfactory in terms of hardness and adhesion to a member.

Such a liquid repellent agent has been used in a variety of industrialfields. For example, in the ink jet field, there has arisen aninconvenience that ink is accumulated on neighborhoods of dischargingoutlets provided in an ink jet head for discharging ink and the ink thusaccumulated possibly causes deviation of the discharging direction ofthe ink and blocks the discharging outlets, and to cope with such aninconvenience, a liquid repellent agent has been applied on a surfaceprovided with the discharging ports (the surface will be hereinafteroccasionally be called a discharging outlet surface).

FIG. 14 is a schematic view showing one example of an ink jet head inwhich a discharging outlet surface is subjected to a liquid repellentfinish using a liquid repellent agent. In FIG. 14, reference numeral 101indicates a substrate for an ink jet head, which is formed of a materialsuch as glass, aluminum or silicon. The substrate 101 is joined with atop plate 102 provided with grooves for forming liquid pathways 104. Theliquid pathways 104 are formed of the grooves of the top plate 102 andthe base plate 101. An energy generating element 103 for discharging inkis provided in each of the liquid pathways 104. A discharging outletplate 107, which is provided with discharging outlets 108 eachcommunicating with the liquid pathways 104 for discharging ink, isjoined with a joined body of the substrate 101 and the top plate 102, toform an ink jet head. A liquid repellent layer 107 a formed of afluorine-based resin is provided on a surface having the dischargingoutlets 108 (hereinafter, referred to as a discharging outlet surface)of the discharging outlet plate 107. The liquid repellent layer 107 ahas a pattern as shown in FIG. 4 in which neighborhoods of thedischarging ports have different liquid repellent properties than theremaining portion. As is well known, the configuration in which a liquidrepellent area extends locally on neighborhoods of discharging outletsand a hydrophilic area 107′ is formed around the liquid repellent areais effective in removal of ink adhering on the discharging outletsurface, as compared with a configuration in which the liquid repellentarea extends over the entire discharging outlet surface.

That is, even in the case where a liquid repellent layer is provided ona discharging outlet surface of an ink jet head, if ink in mist adhereson the discharging outlet surface, it possibly remains thereon. Ingeneral, the ink remaining on the discharging outlet surface is removedby a wiping operation using a cleaning blade; however, if the inkremaining on the discharging outlet surface is thickened in viscosity,the removal of the ink using the cleaning blade becomes difficult. Whenthe ink thickened in viscosity is located on neighborhoods of thedischarging outlets, the ink accumulated thereon is liable to causedeviation of the discharging direction of ink and to block thedischarging outlets. For this reason, the discharging outlet surface isso configured that it has a liquid repellent area around the dischargingoutlets and a hydrophilic area around the liquid repellent area formoving the ink remaining on the discharging outlet surface to thehydrophilic area. This makes it possible to at least reduce thepossibility that the ink remains around the discharging outlets and toeasily collect the ink in small droplets to the hydrophilic area, andhence to facilitate the removal of the ink using the cleaning blade.

In this way, the liquid repellent agent applied on a discharging outletsurface of an ink jet head needs to have a desired adhesion property, adesired rigidity (that is, hardness), and a desired wear resistance.From this viewpoint, a fluorine based resin used as the abovementionedliquid repellent agent does not adequately satisfy the needs regardinghardness and adhesion to a member. On the other hand, Japanese PatentLaid-open No. Hei 4-211959 discloses an ink jet head having adischarging outlet surface subjected to a liquid repellent finish usinga liquid repellent agent composed of a polymer having afluorine-containing heterocyclic structure at a main chain. Thedischarging outlet surface subjected to a liquid repellent finish usingthe above polymer is excellent in liquid repellent property and alsorelatively excellent in wear resistance. It is to be noted that thepolymer having a fluorine-containing heterocyclic structure at a mainchain is being practically used at present as a liquid repellent agentfor a discharging outlet surface of an ink jet head.

It is understood from the above description that the polymer having afluorine-containing heterocyclic structure at a main chain is effectiveas a liquid repellent agent used for subjecting a discharging outletsurface of an ink jet head to a liquid repellent finish.

The polymer, however, does not adequately satisfy the needs in all casesas will be described below.

That is, in recent years, a variety of cartridge type ink jet heads havebeen commercially available for eliminating the necessity of maintenancefor the ink jet head. Such a cartridge type ink jet head (hereinafter,referred to as an ink jet head cartridge) adopts a configuration thatthe discharging outlet surface is protected with a discharging outletsurface protecting member such as a sealing tape or a cap. Thedischarging outlet protecting member is removed when the ink jet headcartridge is mounted on the ink jet system. Accordingly, for an ink jethead cartridge of a type being exchanged in accordance with the colorand physical property of printing ink used, the exchanging operation ofthe ink jet head cartridge is conducted with the discharging outletsurface exposed. Upon this exchanging operation, the discharging outletsurface of the ink jet head cartridge is often brought in contact withthe user's finger, the ink jet system and/or a head cartridge storagevessel. In the case where the discharging outlet surface of such an inkjet head cartridge is provided with a liquid repellent layer formed of aliquid repellent agent composed of the polymer having afluorine-containing heterocyclic structure at a main chain, the liquidrepellent layer is relatively excellent in wear resistance in theconventional service; however, since liquid repellent layer is formed ofthe polymer having a low hardness, it withstands the friction due to thewiping operation but it is possibly scratched when being brought incontact with the above-mentioned obstacles. If the liquid repellentlayer is not directly scratched, there is a possibility thatcontaminants and the like adhere on the discharging outlet surface, andconsequently the liquid repellent layer may be damaged when thecontaminants adhering on the discharging outlet surface are pressed onthe liquid repellent layer by the cleaning blade upon wiping operation.

On the other hand, in recent years, there has been proposed an ink jetsystem for conducting precise printing using ink in a relatively smalldroplet so as to further improve the quality of a printing image. Insuch an improved ink jet system using ink in a relatively small droplet,the distance between the discharging outlet surface and the recordingmedium such as a paper sheet is made very narrow for increasing theshooting accuracy. In the case where the distance between thedischarging outlet surface and the recording medium is narrow, if thereis a slight failure in carrying the recording medium, the dischargingoutlet surface may be rubbed with the recording medium, thereby damagingthe discharging outlet surface. From this viewpoint, the dischargingoutlet surface of the above-mentioned ink jet system needs to beprovided with a liquid repellent layer formed of a liquid repellentagent having such a high hardness that the liquid repellent layer is notdamaged even if it is rubbed with a recording medium.

However, most of the fluorine based resins commonly used for the liquidrepellent agent are relatively low in hardness.

Incidentally, a liquid repellent layer having a large thickness isadvantageous in that when the liquid repellent layer is damaged, it hasa non-damaged portion under the damaged surface portion, so that it ispossible to prevent the deviation of the discharging direction of theink. However, since the liquid repellent agent composed of a polymerhaving a fluorine-containing heterocyclic structure at a main chain isrelatively low in adhesion property, the formation of a very thickliquid repellent layer causes a problem that the liquid repellent layerpeels off. Accordingly, the liquid repellent agent used for forming aliquid repellent layer on a discharging outlet surface of an ink jethead is required to have a characteristic capable of suitablycontrolling the film thickness as well as an excellent film formability.

In this way, the conventional liquid repellent agent cannot makecompatible the hardness with the liquid repellent property at a highlevel, and cannot adequately satisfy the above-mentioned requirements.

European Patent Laid-open No. 631869 discloses a process of imparting aliquid repellent function on a discharging outlet surface locally atneighborhoods of discharging outlets. This process is carried out by amanner of forming a liquid repellent film over the entire dischargingoutlet surface using a solvent-drying type liquid repellent agent, andpartially cutting off the liquid repellent film on the dischargingoutlet surface by way of irradiation of an excimer laser beam, therebyforming a liquid repellent pattern in which a liquid repellent area islocally formed only on neighborhoods of the discharging outlets and ahydrophilic area is formed around the liquid repellent area. However,since a polymer used as the liquid repellent agent has afluorine-containing heterocyclic structure at a main chain and is low inenergy absorbing efficiency for excimer laser, it has a difficulty information of a fine patterning. On the other hand, Japanese PatentLaid-open No. Hei 5-124199 discloses a process in which a photosensitiveresin having a liquid repellent property is formed as a liquid repellentagent on a discharging outlet surface, and is patterned usingphotolithography so that a liquid repellent function is imparted on thedischarging outlet surface locally at neighborhoods of dischargingoutlets. This process is advantageous in that a fine local liquidrepellent pattern can be formed, and that even when the dischargingoutlet surface is subjected to a liquid repellent finish after formationof discharging outlets, liquid repellent agent does not remain in thedischarging outlets.

As for the known photosensitive resins having liquid repellentproperties, including the liquid repellent agent (that is,photosensitive resin) described in Japanese Patent Laid-open Hei5-124199, if they are excellent in their initial liquid repellentproperties, they cannot sufficiently keep the liquid repellentproperties for a long period of time. The reason for this may beconsidered to be due to low hardness of the photosensitive resins as theliquid repellent agents. That is, an area formed of the photosensitiveresin having a low hardness is gradually abraded with the repeatedwiping operations using a cleaning blade for cleaning dischargingoutlets.

As described above, the conventional liquid repellent agents are notsuitable for formation of a local area excellent in liquid repellentproperty, hardness (that is, wear resistance), and adhesion property. Inview of the foregoing, it has been required to provide a liquidrepellent agent for forming a film having a local repellent function andhaving excellent hardness (that is, wear resistance) and adhesionproperty, particularly, at neighborhoods of discharging outlets on adischarging outlet surface of an ink jet head

SUMMARY OF THE INVENTION

An object of the present invention is to provide an epoxy resin basedcomposition useful for a variety of applications, which is readilysoluble in commonly used solvents, exhibits such a compatible state ofcomponents that the components cannot be distinguished at a visiblelight level, and is excellent in hardness, liquid repellent property,adhesion property, and film formability.

Another object of the present invention is to provide an epoxy resinbased composition capable of forming a high quality liquid repellentfilm excellent in liquid repellent property, adhesion property, andsurface properties (hardness and smoothness).

A further object of the present invention is to provide an epoxy resinbased composition capable of reforming a surface of a member into asurface excellent in liquid repellent property, adhesion property, andsurface properties (hardness and smoothness).

A still further object of the present invention is to provide an epoxyresin based composition capable of forming a high quality liquidrepellent film excellent in liquid repellent property, adhesionproperty, and surface properties (hardness and smoothness) on a surfaceof a member in a given shape.

A specific object of the present invention is to provide an epoxy resinbased composition capable of forming a liquid repellent film excellentin surface properties (hardness and smoothness), liquid repellentproperty, and adhesion property on a discharging outlet surface of anink jet head.

Another specific object of the present invention is to provide an epoxyresin based composition capable of forming a liquid repellent resinexcellent in surface properties (hardness and smoothness), liquidrepellent property, and adhesion property on a discharging outletsurface of an ink jet head in a given shape.

To attain the above objects, the present inventors have made thefollowing examination. That is, since any conventional single liquidrepellent agent has failed to attain the above objects as describedabove, the present inventors have attempted to develop a new resincomposition capable of attaining the above object, and as such a resincomposition, the present inventors have adopted a type in whichcomponents of the resin composition are in a compatible state for makinguniform the performance of the resin composition. Here, the compatiblestate means such a state in which components are uniformly mixed andcannot be distinguished at a visible light level. The term “compatiblestate” used hereinafter means such a state as described above.

The present inventors have decided to use an epoxy resin as the basiccomponent of the resin composition in terms of reactivity andworkability, and have extensively studied through experiments to obtaina resin composition capable of attaining the above objects by impartinga liquid repellent property to an epoxy resin as the basic component ofthe resin composition. In the experiments, the examination was madeusing a hardening catalyst in place of a hardening agent for making fulluse of the epoxy resin. First, commercially available liquid repellentagents were used for imparting a liquid repellent property to an epoxyresin; however, these agents were not hardened because they did not cometo be compatible with an epoxy resin. Next, compounds containing F andSi were used for imparting a liquid repellent property to an epoxyresin; however, they failed to obtain a resin composition capable ofattaining the above objects although some compounds come to becompatible with an epoxy resin. The reason for this is that a compoundcontaining F and Si compatible with an epoxy resin has an epoxy group ora functional group reactive with an epoxy group at a terminal, andconsequently, if it comes to be compatible with an epoxy resin, the Sior F group is held between functional groups such as benzene rings,epoxy groups or hydroxyl groups and thereby the liquid repellentcharacteristic of the Si or F group is suppressed. At all events, it hasbeen found that a compound having a Si or F group at a terminal isrequired to be used as a liquid repellent imparting agent. However,since the compound having a Si or F at a terminal is not compatible withan epoxy resin as described above, and from this viewpoint, the presentinventors have examined a compound containing a F or Si group at aterminal which can be compatible with a composition of an epoxy resinand a compound containing a Si or F group and compatible with an epoxyresin. As a result, it has been found that an epoxy compound having aperfluoro group at a terminal is desirable as an agent for imparting aliquid repellent property to an epoxy resin. The present inventors haveexperimentally examined resin compositions containing theabove-mentioned components, and found that a resin composition havingthe following configuration can attain the above objects. That is, theepoxy resin composition capable of attaining the above objects at leastcontains (a) a polyfunctional epoxy resin having two or more epoxygroups in one molecule and not containing F and Si; (b) an epoxycompound having a perfluoro group at a terminal; and (c) a compoundhaving two or more of one kind of two or more kinds selected from anepoxy group, an alcohol group, carboxylic acid group, and an amine groupand containing F or Si.

Since the fluorine-containing epoxy resin composition contains an epoxybased resin as a basic component, that is, the component (a), it isexcellent in adhesion to a member and can be hardened at a relativelylow temperature, and therefore, it provides a hardened structureexcellent in physical properties. Also since the resin compositioncontains an epoxy compound having a perfluoro group at a terminal as thecomponent (b), it can exhibit an excellent liquid repellent property.Further, the resin composition contains the component (c) which makes itpossible to make compatible the component (a) with the component (b) ata desirable mixing ratio. Therefore, the resin composition can provide ahardened resin structure excellent in liquid repellent property,hardness and adhesion property. More specifically, the resin composition(that is, fluorine-containing epoxy resin composition) containing thecomponents (a), (b) and (c) exhibits a desirable compatible state whichcan be kept even when being added with a polymerizing agent and ahardening agent, and it enables formation of a high quality hardenedresin structure excellent in liquid repellent property, hardness, andadhesion property.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 to 12 are views showing basic steps of producing an ink jet headaccording to an embodiment of the present invention;

FIG. 13 is a view showing one example of an ink jet system in which theink jet head having the configuration shown in FIG. 12 is incorporated;and

FIG. 14 is a schematic view showing one example of an ink jet head inwhich a discharging outlet surface is subjected to a liquid repellenttreatment using a known liquid repellent agent.

DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS

A fluorine-containing epoxy resin composition as a basic feature of thepresent invention will be first described.

The fluorine-containing epoxy resin composition of the present inventionat least contains (a) a polyfunctional epoxy resin having two or moreepoxy groups in one molecule and not containing F and Si, (b) an epoxycompound having a perfluoro group at a terminal, and (c) a compoundhaving in one molecule two or more of one kind or two or more kindsselected from an epoxy group, alcohol group, carboxylic acid group, andamine group.

The component (a) of the fluorine-containing epoxy resin composition ofthe present invention is composed of an epoxy resin which is a basiccomponent for giving adhesion to a member and a mechanical strength as astructure to the resin composition. As the epoxy resin of the component(a), there is used a polyfunctional epoxy resin having two or more epoxygroups in one molecule and not containing F and Si. Specific examples ofsaid epoxy resin may include bisphenol A type, bisphenol F type,bisphenol AD type, phenol novolac type, cresol novolac type, alicyclictype, aliphatic type, naphthalene type, and biphenyl type epoxy resins.Such an epoxy resin is commercially available, for example, under thetrade name of Epikote 828 (produced by Yuka Shell Epoxy KabushikiKaisha), Araldite CY179 (produced by Ciba-Geigy Japan Limited), orEHPE-3158 (produced by Daicel Chemical Industries, Ltd.). The component(a) of the fluorine-containing epoxy resin composition is preferably ina range of from 10 to 80 parts by weight. When the content of thecomponent (a) is less than 10 parts by weight, the resin compositioncannot exhibit sufficient performance in terms of adhesion property to amember and mechanical strength as a structure. On the other hand, whenthe content of the component (a) is more than 80 parts by weight, theresin composition becomes insufficient in liquid repellent property.

The component (b) of the fluorine-containing epoxy resin compositionimparts a liquid repellent property to the resin composition, and itcomes to be in a compatible state with the component (a) and thecomponent (c) which will be described later. The component (b) is, asdescribed above, composed of an epoxy compound having a perfluoro groupat a terminal. Specific examples of said epoxy compound may include3-(2-perfluorohexyl) ethoxy-1,2-epoxypropane, andN-propyl-N-(2,3-epoxypropyl) perfluorooctanesulfonamide. Such an epoxycompound is commercially available, for example, under the trade name ofMF-120, MF-130 (produced by TOHKEM PRODUCT CORPORATION). The content ofthe component (b) is preferably in a range of from 10 to 40 parts byweight. When the content of the component (b) is less than 10 parts byweight, the resin composition becomes insufficient in liquid repellentproperty; and when it is more than 40 parts by weight, the resincomposition fails to obtain a sufficient hardness because of theincreased monofunctional component in the resin composition.

The component (c) of the fluorine-containing resin composition functionsto preferably make compatible the components (a) and (b) with eachother, and it is composed of a compound having in one molecule two ormore of one kind or two or more kinds selected from an epoxy group,carboxylic acid group, and an amine group. Specific examples of saidcompound may include2,2-bis[p-(2,3-epoxypropoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane;1,4-bis(hexafluoro-2-hydroxy-2-propyl)benzene;1,3-bis(glycidoxypropyl)tetramethyldisiloxane; and flourohexanediol.Such a compound is commercially available, for example, under the tradename of CHEMINOX AFEp (produced by Nippon Mektron, Ltd.), 1,4-HFAB(produced by Central Glass Co., Ltd.), or LS7970 (produced by Shin-EtsuChemical Co., Ltd.). The content of the component (c) is preferably in arange of from 10 to 80 parts by weight. When the content of thecomponent (c) is less than 10 parts by weight, the resin compositionbecomes insufficient in hardness because the component (c) does not makecompatible the component (b) with the component (a); and when it is morethan 80 parts by weight, the resin composition is insufficient not onlyin liquid repellent property but also in hardness.

In addition, in view of improving resistance to ink, it is morepreferable that, of the above resins as the component (c), the compoundhaving two or more epoxy groups in one molecule and containing F or Siis used in combination with the compound having in one molecule two ormore of one kind or two or more kinds selected from alcohol group,carboxylic acid group, and an amine group and containing F or Si; andthat the mixing ratio between the former compound and the lattercompound is in a range of from 1:5 to 5:1 in weight %.

In the fluorine-containing epoxy resin composition containing thespecified components (a), (b) and (c) in a specified composition, thethree components (a), (b) and (c) are uniformly mixed with each otherinto a desirable compatible state. The fluorine-containing epoxy resincomposition is readily soluble in commonly used solvents, and further,it can keep the above compatible state even when added with apolymerizing catalyst or a hardening agent (hereinafter, referred to asa component (d)).

The fluorine-containing epoxy resin composition of the presentinvention, therefore, can be applied to surface treatment for variousobjects, and can desirably impart a high quality liquid repellent filmexcellent in hardness and adhesion property onto the surfaces of theobjects.

A polymerizing catalyst or hardening agent as the component (d) added tothe resin composition composed of the components (a), (b) and (c) can besuitably selected in accordance with the kind of the object to betreated or the application of the object. In any case, however, thecomponent (d), that is, a polymerizing catalyst or hardening agent isdesired to be uniformly mixed with the fluorine-containing resincomposition and to keep the above-mentioned compatible state of theresin composition. The content of the component (d) is preferably in arange of from 0.1 to 5 parts by weight.

The polymerizing catalyst used as the component (d) is selected to havea function of hardening the resin composition composed of the components(a), (b) and (c). The polymerizing catalyst may be of either athermosetting type or a photosetting type. Specific examples of thepolymerizing catalyst may include boron trifluoride-amine complex, bis(4-t-butylphenyl) iodonium salt, and Cu(CF₃SO₃)₂. Such a polymerizingcatalyst is commercially available, for example, under the trade name ofSP170 (produced by Asahi Denka Kogyo K.K.).

A hardening agent used as the component (d) is selected to be of athermosetting type functioning as a thermosetting catalyst and hardeningthe resin composition composed of the components (a), (b) and (c). Asthe hardening agent of a thermosetting catalyst type, there may be usedan amine based hardening agent and an acid anhydride type hardeningagent, and preferably, an amine compound containing a siloxane group ora perfluoro group, and an acid anhydride of the amine compound. Specificexamples of the hardening agent may include α,ω-bis (3-aminopropyl)polydimethyl siloxane (trade name: TSL9346, produced by Toshiba SiliconeCo., Ltd.); 1,3-bis (3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (tradename: LS-7430, produced by Shin-Etsu Chemical Co. Ltd.); and 2,2-bis(4-aminophenyl)-hexafluoropropane (trade name: BIS-A-AF, produced byCentral Glass Co., Ltd.).

In addition, the fluorine-containing epoxy resin composition of thepresent invention may contain, in addition to the components (a) to (d),a known silane coupling agent or leveling agent, as required.

Other than the above, a filler such as quartz talc or a pigment may beadded, as required.

The fluorine-containing epoxy resin composition of the present inventionincludes two types: one having a flowability at normal temperature, andthe other having no flowability at normal temperature. Thefluorine-containing epoxy resin composition of a type having aflowability at normal temperature can be directly used for filmformation; however, in order to make the components of the resincomposition in a desirable compatible state, it is desired that thecomponents be dissolved in a solvent and used for film formation byevaporation of the solvent. For example, in the case of forming a filmof the fluorine-containing epoxy resin composition by way of a coatingprocess, the components of the resin composition are dissolved in asolvent, and a surface of an object is coated with the solution thusobtained using a solvent coating process such as a spin coating process,followed by evaporation of the solvent, to form a high quality film onthe surface of the object to a uniform thickness.

Since the fluorine-containing epoxy resin composition of the presentinvention can be dissolved in most of solvents commonly used for knownepoxy resins, there can be used known solvents such as acetone,methylisobutyl ketone, diethyleneglycol dimethyl ether, cyclohexane.Also such a solvents are for is commercially available, for example,under the trade name of Solvesso (produced by Dainippon Ink & Chemicals,Incorporated). It is to be noted that these solvent are illustrativepurposes only and are not restrictive.

The fluorine-containing epoxy resin composition of the present inventioncomposed of the above-mentioned components can be hardened at arelatively low temperature, to form a hardened structure excellent inadhesion property, weatherability, water tightness, chemical resistance,solvent resistance, friction resistance, and liquid repellent property.

The fluorine-containing epoxy resin composition of the present inventioncan be suitably used for treating a specified surface of a member ordevice so as to impart a liquid repellent property thereto, and also itcan be used for adhesively bonding members to each other. In addition,the fluorine-containing epoxy resin composition of the present inventioncan be used as a paint by adding and diffusing a coloring material inthe resin composition.

The fluorine-containing epoxy resin composition of the present inventionis particularly suitable as a material for forming a liquid repellentlayer on a discharging outlet surface of an ink jet head.

Hereinafter, description will be made of an example of an ink jet headin which a discharging outlet surface is subjected to a liquid repellentfinish using the fluorine-containing epoxy resin composition of thepresent invention.

An example of producing an ink jet head of the present invention will bedescribed with reference to the drawings. FIGS. 1 to 12 show basic stepsof producing an ink jet head. In these figures, there is shown an inkjet head having two discharging outlets; however, this is forsimplification purposes only. It should be understood that the ink jethead of the invention includes a high density multi-array type ink jethead having three or more discharging outlets and also an ink jet headhaving only one discharging outlet.

FIG. 1 is a schematic perspective view of a substrate 1 for an ink jethead which is used for production of an ink jet head in this embodiment.

As shown in FIG. 1, there is prepared the substrate 1 formed of anappropriate material selected from silicon, glass, ceramics, plasticsand metals. The substrate 1 may serve not only as an ink pathwaywall-forming member but also as a support for a coating resin layerwhich will be described later, and it is not particularly limited interms of shape and material thereof.

The substrate 1 is provided with a plurality of energy generatingelements 2 which are spacedly arranged at equal intervals on the surfacethereof. The energy generating element 2 is represented by anelectrothermal converting element or piezo-electric element. In FIG. 1,there are shown only two energy generating elements, but this is forsimplification purposes only. In practice, a number of energy generatingelements are usually arranged on the substrate 1. Each energy generatingelement 2 serves to impart energy to ink in an ink pathway fordischarging ink in a droplet from a discharging outlet so as to providean image on a printing medium such as a paper. In particular, in thecase where an electrothermal converting element is used as the energygenerating element 2, the electrothermal converting element generatesthermal energy to heat ink in the vicinity thereof, thereby causing astate change for the ink to form a bubble, wherein energy generatedbased on a pressure change caused upon the formation of the bubbleeffects as discharging energy to result in discharging ink in a dropletfrom a discharging outlet. In the case where a piezo-electric element isused as the energy generating element, energy caused by the mechanicalvibration of the piezo-electric element effects as discharging energy todischarge ink in a droplet from a discharging outlet.

In any case, the energy generating element 2 includes a control signalinputting electrode electrically connected thereto (not shown).

The substrate 1 may contain a proper functional layer, disposed on theenergy generating element 2, for improving the durability thereof.

In addition, as shown in FIG. 1, the substrate 1 is provided with an inksupply port 3 comprising a through hole which is disposed at a positionof the substrate where no energy generating element is present.

Then, as shown in FIG. 2, a photosensitive resin layer 4 is formed onthe substrate 1 for an ink jet head in a manner to cover the energygenerating elements 2 disposed on the substrate 1. The photosensitiveresin layer 4 may be formed of a positive type photosensitive resin inview of patterning characteristic and solubility. The formation of thephotosensitive resin layer 4 may be conducted by a manner of providing asolution of the photosensitive resin dissolved in a given solvent,applying the solution on a proper film such as a PET film to form aliquid coat on the film, converting the liquid coat on the film into adry film, and transferring the dry film onto the substrate 1 for an inkjet head by using a laminator.

Alternatively, the formation of the photosensitive resin layer 4 may beconducted by means of the solvent-coating process such as a spin coatingor roll coating process. In this formation process, the ink supply port3 is formed by anisotropic etching in a state in which a coating resinlayer 6 is provided on the substrate 1.

Then, as shown in FIG. 3, a patterning mask 5 is superposed on thesurface of the photosensitive resin layer 4, and active energy radiationsuch as ultraviolet radiation or ionizing radiation is irradiated ontothe photosensitive resin layer 4 using a patterning mask 5 having apattern allowing the irradiation for a predetermined portion which doesnot contribute to the formation of an ink pathway to solubilize thepredetermined portion, followed by eluting with the use of a solvent toremove the predetermined portion, thereby forming an ink pathway-formingpattern 4 a as shown in FIG. 4. The ink pathway-forming pattern 4 a iscomprised of the non-solubilized photosensitive resin. The inkpathway-forming pattern 4 a contributes to the formation of an inkpathway provided with the ink supply port 3 and energy generatingelements 2 (see FIG. 4).

After the formation of the ink pathway-forming pattern 4 a, as shown inFIG. 5, a coating resin layer 6 is formed on the ink pathway-formingpattern 4 a in a manner to cover the ink pathway-forming pattern 4 a.The coating resin layer 6 serves as a structural member of an ink jethead, and therefore, it is required to have sufficient mechanicalstrength, heat resistance, adhesion property to the substrate 1, andresistance to ink. As the constituent material of the coating resinlayer 6 which satisfies these requirements, there can be used hardeningresins such as epoxy resin, acrylic resin, diglycol dialkylcarbonateresin, unsaturated polyester resin, diarylphthalate resin, polyurethaneresin, polyimide resin, melamine resin, phenol resin, and urea resin.These hardening resins are used together with a conventional hardeningagent upon forming the coating resin layer. If necessary, it is possibleto use light or thermal energy in order to harden any of these hardeningresins by which the coating resin layer is constituted.

The formation of the coating resin layer 6 may be conducted by a mannerof providing a solution of any of the above hardening resins dissolvedin a given solvent and applying the solution onto the inkpathway-forming pattern 4 a by the solvent-coating process or anothermanner of heat-fusing any of the above hardening resins to obtain afused resin and applying the fused resin onto the ink pathway-formingpattern by way of transfer molding.

After the formation of the coating resin layer 6, discharging outletsare formed in the coating resin layer by way of lithography. Theformation of the discharging outlets may be conducted, for example, inthe following manner.

That is, in the case of forming the discharging outlets byphotolithography, the coating resin layer is constituted by a hardeningresin having a negative photosensitive property. Then, as shown in FIG.6, the coating resin layer 6 is subjected to light exposure through adischarging outlet-forming patterning mask 7 having shielding portionsfor forming discharging outlets. The coating resin layer is thushardened except for its shielded portions to form a dischargingoutlet-forming pattern in the coating resin later, wherein thedischarging outlet-forming pattern comprises non-hardened portions basedon the shielded portions and the remaining portion of the coating resinlayer is hardened. Thereafter, as shown in FIG. 7, the non-hardenedportions are removed by eluting them with the use of a solvent, therebyforming discharging outlets 9 in the coating resin layer 6.

In this embodiment, the formation of the discharging outlets isconducted before the solubilization of the ink pathway-forming portionof the photosensitive resin layer 4. This is due to the fact that sincethe coating resin layer is constituted by the negative typephotosensitive resin, if the irradiation of ionizing radiation to theink pathway-forming portion of the photosensitive layer 4 should beconducted in advance of the formation of the discharging outlets, thedischarging outlet-forming portions of the coating resin layer 6 arehardened so that no discharging outlet can be formed.

In this embodiment, the ink discharging outlets 9 are formed usingphotolithography; however, they may be formed by a manner of superposinga mask having a discharging outlet-forming pattern on the coating resinlayer, followed by irradiation by excimer laser beam or dry etchingusing oxygen plasma. In addition, in the case where discharging outletsare formed using oxygen plasma or excimer laser, it is necessary toharden the coating resin layer.

Then, as shown in FIG. 8, in order to form a liquid repellent layer onthe discharging outlet surface, a liquid repellent agent composed of thefluorine-containing epoxy resin composition of the present invention isapplied on the coating resin layer 6 provided with the dischargingoutlets (discharging outlet surface) by way of a solvent coating processsuch as a spin coating process, to form a liquid repellent layer 10.

The liquid repellent layer 10 is then patterned for locally imparting aliquid repellent function only on neighborhoods of the dischargingoutlets. The patterning of the liquid repellent layer 10 can beconducted by photolithography, and for this purpose, aphoto-polymerizing catalyst is used as the component (d) of thefluorine-containing epoxy resin composition. The patterning of theliquid repellent layer by photolithography is conducted, for example, inthe following manner.

First, as shown in FIG. 9, the liquid repellent layer having a negativephotosensitive characteristic is exposed through a patterning mask 11having such a pattern as to allow active energy radiation to passthrough only the neighborhoods of the discharging outlets. The exposedportion of the liquid repellent layer 10 is hardened, so that the otherportion than the neighborhoods of the discharging outlets is patternedin a desired state. Then, as shown in FIG. 10, the non-exposed portionof the liquid repellent layer 10 is eluted by a solvent, to form aliquid repellent pattern 10 a extended only on the neighborhoods of thedischarging outlets.

Next, as shown in FIG. 11, ionizing irradiation is irradiated on the inkpathway-forming portion 4 a through the liquid repellent pattern 10 aand the coating resin layer 6, to solubilize the ink pathway-formingportion 4 a.

Finally, the ink pathway-forming pattern 4 a thus solubilized is elutedwith a solvent, to form an ink pathway 8. An ink jet head shown in FIG.12 is thus obtained.

In the above, description has been made of the case of providing theside shooter type ink jet head. However, it is a matter of course thatthe present invention can be employed also for production of an ink jethead of the edge shooter type of discharging ink in the direction alongthe face on which energy generating elements are arranged. In the casewhere the present invention is employed for production of the edgeshooter type ink jet head, discharging outlets are formed at an endportion of the substrate for an ink jet head having the coating resinlayer formed thereon and therefore, the above discharging outlet-formingstep is not necessary to be conducted.

In the ink jet head of this embodiment, the hardened layer (liquidrepellent pattern) of the hardened fluorine-containing epoxy resincomposition is locally provided on the discharging outlet surface atleast at neighborhoods of the discharging outlets, so that theneighborhoods of the discharging outlets are given a liquid repellentproperty, and accordingly, it is possible to prevent droplets (inkdroplets) from adhering on the discharging outlet surface and hence toprevent deviation of the discharging direction of ink. Also, thehardened layer is excellent in adhesion property. In addition, a fineliquid repellent pattern can be formed only on the neighborhoods of thedischarging outlets using the fluorine-containing epoxy resincomposition of the present invention.

FIG. 13 shows one example of an ink jet system in which an ink jet headhaving the configuration shown in FIG. 12 is incorporated. In FIG. 13,reference numeral 61 indicates a blade as a wiping member, which is heldin a cantilever manner with one end fixedly held on a blade holdingmember. The blade 61 is disposed at a position adjacent to a printingregion from an ink jet head 65, and is held in a manner to project in amovement path of the ink jet head 65.

Reference numeral 62 indicates a cap disposed at a home positionadjacent to the blade 61, which is moved in the direction perpendicularto the movement direction of the ink jet head 65 so as to be abutted onthe discharging outlet surface for capping it. Reference numeral 63indicates an ink absorber provided adjacently to the blade 61, which isheld in a manner to project in the moving path of the ink jet head 65like the blade 61. The blade 61, cap 62, and the ink absorber 63 serveto remove water content, dust and the like from the ink dischargingoutlet surface.

The ink jet head 65 is configured to discharge recording liquid (ink) bythermal energy. Reference numeral 66 indicates a cartridge for movingthe ink jet head 65 mounted thereon. The cartridge 66 is movable along aguide shaft 67 to the printing region in which printing is conducted bythe ink jet head 65 and to the resin adjacent thereto.

Reference numeral 51 indicates a paper feeder in which a printing mediumis inserted, and 52 indicates a paper feed roller driven by a motor (notshown). With this configuration, the printing medium is fed to aposition opposed to the discharging outlet surface of the ink jet head65, and is discharged by means of a discharging roller 53 as theprinting proceeds.

With this configuration, when the ink jet head 65 is returned to thehome position after completion of printing or the like, the cap 62 of ahead recovery unit 64 is retreated from the moving path of the ink jethead 65, but the blade 61 projects in the moving path for wiping thedischarging outlet surface of the ink jet head 65. When the cap 62 isabutted on the discharging outlet surface of the ink jet head 65 forcapping it, it is moved so as to project in the moving path of the inkjet head 65.

When the ink jet head 65 is moved from the home position to the printingstarting position, the cap 62 and the blade 61 are located at the samepositions as those upon wiping operation. As a result, even at such amovement of the ink jet head 65, the discharging outlet surface of theink jet head 65 is wiped. The ink jet head 65 is moved to the homeposition not only after completion of recording and in the stand-bycondition for discharging recovery but also at specified intervalsduring movement in the printing region for printing.

Color printing is conducted using an ink jet head having dischargingoutlets for cyan, magenta, yellow, and black which are arranged inparallel to each other, or using ink jet heads for cyan, magenta, yellowand black which are arranged in parallel to each other. In this case,the discharging of each color ink may be conducted only through onedischarging outlet or the discharging of respective color inks may beconducted through a plurality of discharging outlets so as to allow thedroplets having two or more of color inks to be simultaneously shot on aprinting medium.

EXPERIMENTS

Hereinafter, there will be described main parts of experiments whichhave been conducted by the present inventors in the course of findingthe above-mentioned fluorine-containing epoxy resin composition of thepresent invention. Sample Nos. 1 to 20 were each prepared in Experiments1 to 20, and were examined in usability on the basis of the measuredresults regarding the hardness, liquid repellent property, adhesionproperty, film formability, and flowability before hardening.

In addition, a plurality of specimens were prepared for each of SampleNos. 1 to 20 corresponding to Experiments 1 to 20.

Experiment 1

First, there was prepared a coating solution by dissolving, inmethylisobutyl ketone, 50 parts by weight of a bisphenol A type epoxyresin “Epikote 828” (trade name, produced by Yuka Shell Epoxy KabushikiKaisha) as the component (a); 20 parts by weight of 3-(2-perfluorohexyl)ethoxy-1,2-epoxypropane “MF-120” (trade name, produced by TOHKEM PRODUCTCORPORATION) as the component (b); 30 parts by weight of 1,3-bis(glycidoxypropyl)tetramethyldisiloxane “LS7970” (trade name, produced byShin-Etsu Chemical Co., Ltd.) as a component (c); and 1.5 parts byweight of a photo-polymerizing initiator “SP-170” (trade name, producedby Asahi Denka Kogyo K. K.) as the component (d), to prepare amethylisobutyl ketone solution in a concentration of 50 wt %. Theresultant methylisobutyl ketone solution in an amount of 2 cc wasdropped on a circular Si wafer having a diameter of 5 inches, followedby spin coating at a rotating speed of 600 rpm for 80 seconds, to coatthe Si wafer with the methylisobutyl ketone solution. The Si wafer wasdried at 80° C. for 15 minutes, being exposed to ultraviolet radiationat an exposure condition of 8 J/cm², and was thermally cured at 180° C.for one hour, to thus obtain Sample 1. In addition, as a result ofobservation of the sample in a state directly after the dryingtreatment, the sample was found to have flowablity.

Experiment 2

In this experiment, Sample 2 was prepared in the same manner as that ofExperiment 1, except that 55 parts by weight of an alicyclic type epoxyresin “CY179” (trade name, produced by Ciba-Geigy, Ltd.) was used as thecomponent (a); 16 parts by weight of the 3-(2-perfluorohexyl)ethoxy-1,2-epoxypropane “MF-120” (trade name, produced by TOHKEM PRODUCTCORPORATION) was used as the component (b); and 21 parts by weight of1,4-bis (hexaflouro-2-hydroxyl-2-propyl) benzene “1,4-HFAB” (trade name,produced Central Glass Co., Ltd.). In addition, as a result ofobservation of the sample in a state directly after the dryingtreatment, the sample was found to have flowablity.

Experiment 3

In this experiment, Sample 3 was prepared in the same manner as that ofExperiment 1, except that 70 parts by weight of the alicyclic type epoxyresin “CY179” (trade name, produced by Ciba-Geigy, Ltd.) was used as thecomponent (a); 10 parts by weight of the 3-(2-perfluorohexyl)ethoxy-1,2-epoxypropane “MF-120” (trade name, produced by TOHKEM PRODUCTCORPORATION) was used as the component (b); 20 parts by weight of2,2-bis [p-(2,3-epoxypropoxy) phenyl]-1,1,1,3,3,3-hexafluoropropane“CHEMINOX AFEp” (trade name, produced by Nippon Mektron, Ltd.) was usedas the component (c). In addition, as a result of observation of thesample in a state directly after the drying treatment, the sample wasfound to have flowablity.

Experiment 4

In this experiment, Sample 4 was prepared in the same manner as that ofExperiment 1, except that 34 parts by weight of alicyclic type epoxyresin “EHPE-3158” (trade name, produced by Daicel Chemical Industries,Ltd.) was used as the component (a); 16 parts by weight of the3-(2-perfluorohexyl) ethoxy-1,2-epoxypropane “MF-120” (trade name,produced by TOHKEM PRODUCT CORPORATION) was used as the component (b);and 25 parts by weight of the 2,2-bis [p-(2,3-epoxypropoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane “CHEMINOX AFEp” (trade name,produced by Nippon Mektron, Ltd.) and 25 parts by weight of the 1,4-bis(hexaflouro-2-hydroxyl-2-propyl) benzene “1,4-HFAB” (trade name,produced by Central Glass Co., Ltd.) were used as the component (c). Inaddition, as a result of observation of the sample in a state directlyafter the drying treatment, the sample was found to lose flowablity.

Experiment 5

First, there was prepared a coating solution by dissolving, inmethylisobutyl ketone, 34 parts by weight of the alicyclic type epoxyresin “EHPE-3158” (trade name, produced by Daicel Chemical Industries,Ltd.) as the component (a); 16 parts by weight ofN-propyl-N-(2,3-epoxypropyl) perfluorooctanesulfonamide “MF-130” (tradename, produced by TOHKEM PRODUCT CORPORATION) as the component (b); 25parts by weight of the 1,4-bis (hexaflouro-2-hydroxyl-2-propyl) benzene“1,4-HFAB” (trade name, produced by Central Glass Co., Ltd.) and 25parts by weight of the 1,3-bis (glycidoxypropyl) tetramethyldisiloxane“LS7970” (trade name, produced by Shin-Etsu Chemical Co., Ltd.) as acomponent (c); and 1 part by weight of a thermosetting catalystCu(CF₃SO₃)₂ as the component (d), to prepare a methylisobutyl ketonesolution in a concentration of 50 wt %. The resultant methylisobutylketone solution in an amount of 2 cc was dropped on a circular Si waferhaving a diameter of 5 inches, followed by spin coating at a rotatingspeed of 600 rpm for 80 seconds, to coat the Si wafer with themethylisobutyl ketone solution. The Si wafer was dried at 80° C. for 15minutes, being exposed to ultraviolet radiation at an exposure conditionof 8 J/cm², and was thermally cured at 180° C. for one hour, to thusobtain Sample 1. In addition, as a result of observation of the samplein a state directly after the drying treatment, the sample was found tohave flowablity.

Experiment 6

In this experiment, Sample 6 was prepared in the same manner as that ofExperiment 4, except that 1 part by weight of the thermosetting catalystCu(CF₃SO₃)₂ was used as the component (d), and the exposure step for thesample was omitted. In addition, as a result of observation of thesample in a state directly after the drying treatment, the sample wasfound to lose flowablity.

Experiment 7

In this experiment, Sample 7 was prepared in the same manner as that ofExperiment 4, except that 20 parts by weight of the 2,2-bis[p-(2,3-epoxypropoxy) phenyl]-1,1,1,3,3,3-hexafluoropropane “CHEMINOXAFEp” (trade name, produced by Nippon Mektron, Ltd.) and 30 parts byweight of flourohexanediol were used as the component (c). In addition,as a result of observation of the sample in a state directly after thedrying treatment, the sample was found to lose flowablity.

Experiment 8

In this experiment, Sample 8 was prepared in the same manner as that ofExperiment 1, except that 40 parts by weight of the bisphenol A typeepoxy resin “Epikote 828” (trade name, produced by Yuka Shell EpoxyKabushiki Kaisha) was used as the component (a); 20 parts by weight ofthe 2,2-bis [p-(2,3-epoxypropoxy) phenyl]-1,1,1,3,3,3-hexafluoropropane“CHEMINOX AFEp” (trade name, produced by Nippon Mektron, Ltd) and 20parts by weight of the 1,3-bis (glycidoxypropyl) tetramethyldisiloxane“LS7970” (trade name, produced by Shin-Etsu Chemical Co., Ltd.) wereused as the component (c). In addition, as a result of observation ofthe sample in a state directly after the drying treatment, the samplewas found to have flowablity.

Experiment 9

In this experiment, the components (a) and (b) were not used. First,there was prepared a coating solution by dissolving, in methylisobutylketone, 100 parts by weight of the 2,2-bis [p-(2,3-epoxypropoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane “CHEMINOX AFEp (trade name,produced by Nippon Mektron, Ltd.) as the component (c) and 1.5 parts byweight of the photo-polymerizing initiator “SP-170” (trade name,produced by Asahi Denka Kogyo K. K.) as the component (d), to prepare amethylisobutyl ketone solution in a concentration of 50 wt %. Then,using the resultant methylisobutyl ketone solution, Sample 9 wasprepared in the same coating and hardening conditions as those inExperiment 1. In addition, as a result of observation of the sample in astate directly after the drying treatment, the sample was found to haveflowablity.

Experiment 10

In this experiment, the components (a) and (c) were not used. First,there was prepared a coating solution by dissolving, in methylisobutylketone, 100 parts by weight of the 3-(2-perfluorohexyl)ethoxy-1,2-epoxypropane “MF-120” (trade name, produced by TOHKEM PRODUCTCORPORATION) as the component (b) and 1.5 parts by weight of thephoto-polymerizing initiator “SP-170” (trade name, produced by AsahiDenka Kogyo K. K.) as the component (d), to prepare a methylisobutylketone solution in a concentration of 50 wt %. Then, using the resultantmethylisobutyl ketone solution, Sample 10 was prepared in the samecoating and hardening conditions as those in Experiment 1. In addition,as a result of observation of the sample in a state directly after thedrying treatment, the sample was found to have flowablity.

Experiment 11

In this experiment, the component (a) was not used. First, there wasprepared a coating solution by dissolving, in methylisobutyl ketone, 20parts by weight of the 3-(2-perfluorohexyl) ethoxy-1,2-epoxypropane“MF-120” (trade name, produced by TOHKEM PRODUCT CORPORATION) as thecomponent (b); 80 parts by weight of the 1,3-bis (glycidoxypropyl)tetramethyldisiloxane “LS7970” (trade name, produced by Shin-EtsuChemical Co., Ltd.) as the component (c); and 1.5 parts by weight of thephoto-polymerizing initiator “SP-170” (trade name, produced by AsahiDenka Kogyo K. K.) as the component (d), to prepare a methylisobutylketone solution in a concentration of 50 wt %. Then, using the resultantmethylisobutyl ketone solution, Sample 11 was prepared in the samecoating and hardening conditions as those in Experiment 1. In addition,as a result of observation of the sample in a state directly after thedrying treatment, the sample was found to have flowablity.

Experiment 12

In this experiment, the component (c) was not used. First, there wasprepared a coating solution by dissolving, in methylisobutyl ketone, 84parts by weight of the produced by Daicel Chemical Industries, Ltd.) asthe component (a); 16 parts by weight of the 3-(2-perfluorohexyl)ethoxy-1,2-epoxypropane “MF-120” (trade name, produced by TOHKEM PRODUCTCORPORATION) as the component (b); and 1.5 parts by weight of thephoto-polymerizing initiator “SP-170” (trade name, produced by AsahiDenka Kogyo K. K.) as the component (d), to prepare a methylisobutylketone solution in a concentration of 50 wt %. Then, using the resultantmethylisobutyl ketone solution, Sample 12 was prepared in the samecoating and hardening conditions as those in Experiment 1. In addition,as a result of observation of the sample in a state directly after thedrying treatment, the sample was found to have flowablity.

Experiment 13

In this experiment, Sample 13 was prepared using only a photo radicalpolymerization type liquid repellent agent “DEFENSA7710” (trade name,produced by Dainippon Ink & Chemicals, Incorporated) in the same coatingand drying conditions as those in Experiment 1. In addition, as a resultof observation of the sample in a state directly after the dryingtreatment, the sample was found to lose flowablity.

Experiment 14

In this experiment, Sample 14 was prepared using only a solvent dryingtype liquid repellent agent composed of a polymer having afluorine-containing heterocyclic structure at a main chain “CTX-805A”(trade name, produced by Asahi Glass Co., Ltd.) in the same coating anddrying conditions as those in Experiment 1. In addition, as a result ofobservation of the sample in a state directly after the dryingtreatment, the sample was found to lose flowablity.

Experiment 15

In this experiment, Sample 15 was prepared in the same manner as that ofExperiment 4, except that 5 parts by weight of the 3-(2-perfluorohexyl)ethoxy-1,2-epoxypropane “MF-120” (trade name, produced by TOHKEM PRODUCTCORPORATION) was used as the photo radical polymerization component (b);31 parts by weight of the 2,2-bis [p-(2,3-epoxypropoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane “CHEMINOX AFEp” (trade name,produced by Nippon Mektron, Ltd.) was used as the component (c); and 30parts by weight of the 1,4-bis (hexaflouro-2-hydroxyl-2-propyl) benzene“1,4-HFAB” (trade name, produced by Central Glass Co., Ltd.) was used asthe component (d). In addition, as a result of observation of the samplein a state directly after the drying treatment, the sample was found tolose flowablity.

Experiment 16

In this experiment, Sample 16 was prepared in the same manner as that ofExperiment 4, except that 5 parts by weight of the alicyclic type epoxyresin “EHPE-3158” (trade name, produced by Daicel Chemical Industries,Ltd.) was used as the component (a) and 54 parts by weight of the2,2-bis [p-(2,3-epoxypropoxy) phenyl]-1,1,1,3,3,3-hexafluoropropane“CHEMINOX AFEp” (trade name, produced by Nippon Mektron, Ltd.) was usedas the component (c). In addition, as a result of observation of thesample in a state directly after the drying treatment, the sample wasfound to have flowablity.

Experiment 17

In this experiment, Sample 17 was prepared in the same manner as that ofExperiment 4, except that 15 parts by weight of the alicyclic type epoxyresin “EHPE-3158” (trade name, produced by Daicel Chemical Industries,Ltd.) was used as the component (a) and 44 parts by weight of the2,2-bis [p-(2,3-epoxypropoxy) phenyl]-1,1,1,3,3,3-hexafluoropropane“CHEMINOX AFEp” (trade name, produced by Nippon Mektron, Ltd.) was usedas the component (c). In addition, as a result of observation of thesample in a state directly after the drying treatment, the sample wasfound to have flowablity.

Experiment 18

In this experiment, Sample 18 was prepared in the same manner as that ofExperiment 1, except that 46 parts by weight of the alicyclic type epoxyresin “CY179” (trade name, produced by Ciba-Geigy, Ltd.) was used as thecomponent (a) and 10 parts by weight of the 1,3-bis (glycidoxypropyl)tetramethyldisiloxane “LS7970” (trade name, produced by Shin-EtsuChemical Co., Ltd.) was used as the component (c). In addition, as aresult of observation of the sample in a state directly after the dryingtreatment, the sample was found to have flowablity.

Experiment 19

In this experiment, Sample 19 was prepared in the same manner as that ofExperiment 4, except that 16 parts by weight of the 3-(2-perfluorohexyl)ethoxy-1,2-epoxypropane “MF-120” (trade name, produced by TOHKEM PRODUCTCORPORATION) as the component (b) in Experiment 4 was replaced with 16parts by weight of 2-perfluorooctaneethylacrylate “CHNIMOX FAAC” (tradename, produced by Nippon Mektron, Ltd.). In addition, as a result ofobservation of the sample in a state directly after the dryingtreatment, the sample was found to have flowablity.

Experiment 20

In this experiment, Sample 20 was prepared in the same manner as that ofExperiment 1, except that 20 parts by weight of Sefral Coat A-101B(trade name, produced by Central Glass Co., Ltd.) was used as thecomponent (b) in place of the 3-(2-perfluorohexyl)ethoxy-1,2-epoxypropane “MF-120” (trade name, produced by TOHKEM PRODUCTCORPORATION). In addition, as a result of observation of the sample in astate directly after the drying treatment, the sample was found to haveflowablity.

EVALUATION

Sample Nos. 1 to 20 obtained in Experiments 1 to 20 were evaluated inthe following manner in terms of hardness, liquid repellent property,adhesion property, and film formability. The results are shown in Table1.

(1) Evaluation of Hardness:

The hardness of each sample was examined by a manner of placing a PPCcopy paper (produced by CANON INC.) on each sample, rubbinglyreciprocating the copy paper on the sample 10 times in a state that aload of 500 gf/cm² is applied on the copy paper, and observing thesurface state of the sample with a microscope. The evaluated results onthe basis of the following reference are shown in Table 1.

(Evaluation Reference)

⊚: no damage

◯: micro-damage not visible, slightly observed

Δ: visible damage

×: separation of film from substrate

(2) Evaluation of Liquid Repellent Property:

The liquid repellent property of each sample was examined by dropping ablack ink for BJC4000 produced by CANON INC. on the sample in an amountof 0.1 cc, erecting the substrate of the sample, and visually evaluatingwhether or not ink remains on the sample. The evaluated results on thebasis of the following reference are shown in Table 1.

(Evaluation Reference)

⊚: ink immediately dropped

◯: ink not immediately dropped but thereafter entirely dropped

×: ink remaining on the sample

(3) Evaluation of Adhesion Property

Each sample was subjected to an ink immersion (PCT) test conducted at121° C. and at 2 atm for 10 hours using the black ink for BJC4000produced by CANON INC. The resultant sample was washed with water,followed by drying, and was examined for adhesion property by observingthe adhesion state of the film of the sample with the Si wafer using amicroscope. The evaluated results on the basis of the followingreference are shown in Table 1.

(Evaluation Reference)

◯: film closely bonded with the substrate in preferable state

Δ: film slightly micro-separated and/or swelled

×: film apparently separated and swelled

(4) Evaluation of Film Formability

The film formability of each sample was examined by observing thesurface condition (surface smoothness) of the film formed on the Siwafer of the sample using a microscope. The evaluated results on thebasis of the following reference are shown in Table 1.

(Evaluation Reference)

◯: no waviness, striped unevenness and aggregation on film surface

×: waviness striped unevenness and aggregation observed on film surface

Other than the above evaluation items, each sample was examined in termsof solvent-suitability (solvent-solubility) of the resin compositionconstituting each sample. The evaluated results on the followingreference are also shown in Table 1.

(Evaluation Reference)

◯: resin composition dissolved in solvents commonly used for ordinarypaint, such as acetone and methylisobutyl ketone

×: resin composition not dissolved in the solvents commonly used forordinary paint

Here, a sample having the solvent-suitability evaluated at the mark (◯)may be regarded to be high in flexibility when used as a paint becauseit allows the solvent to be suitably selected in consideration of thematerial and shape of the coating surface and also allows a levelingagent and an antifoaming agent commonly used for a paint to be addedthereto.

The total evaluation for each sample was conducted by totally evaluatingthe evaluated results in the above evaluation items on the basis of thefollowing reference. The results are also shown in Table 1.

(Evaluation Reference)

⊚: (⊚ or ◯) in all evaluation items

◯: only (◯) in all evaluation items

Δ: not including (X) but including (Δ) in at least one item

×: including (X) in at least one item

Hereinafter, the evaluation for the samples will be concretely describedwith reference to Table 1. Here, Sample Nos. 1 to 8, and 17 pertain tothe present invention.

From the results shown in Table 1, it is revealed that each of SampleNos. 1 to 8, and 17 according to the resin composition of the presentinvention is excellent in hardness, liquid repellent property, adhesionproperty, film formability, and solvent-suitability, and therefore, itis suitable as a liquid repellent agent used when a discharging outletsurface of an ink jet head is subjected to a liquid repellent finish.

In particular, each of Sample Nos. 1 to 8 is significantly excellent inhardness as compared with the conventional liquid repellent agent, andtherefore, in the case where the resin composition of each of SampleNos. 1 to 8 is used as a liquid repellent agent for imparting a liquidrepellent function onto a discharging outlet surface of an exchangeabletype ink jet head cartridge, there can be realized the ink jet headcartridge excellent in the reliability and printing quality.

Table 1 also shows that Sample No. 9 does not have a desired performancein terms of liquid repellent property and adhesion property. The poorliquid repellent property of Sample No. 9 may be considered to be due tothe structure of the 2,2-bis [p-(2,3-epoxypropxy)phenyl]-1,1,1,3,3,3-hexafluoropropane “CHEMINOX AFEp” (trade name,produced by Nippon Mektron, Ltd.) in which a perfluoro group having aliquid repellent function is held between benzene rings and thereby itcannot exhibit the characteristic thereof.

Samples Nos. 10 to 12, and 19 and 20, as shown in Table 1, could beevaluated in hardness, liquid repellent property, adhesion property, andfilm formability because the film forming materials were not hardened.In addition, each of Sample Nos. 12, 19 and 20 was observed to be cloudybecause the components used did not come to be in a compatible state.

Table 1 shows that Sample Nos. 13 and 14 are excellent in liquidrepellent property but are insufficient in adhesion property andsolvent-suitability.

From the results shown in Table 1, it is understood that Sample No. 15is poor in liquid repellent property. The reason for this is that thecontent of the component (b) for imparting the liquid repellent functionis low.

As is apparent from Table 1, Sample No. 16 is poor in adhesion propertyand film formability and is insufficient in hardness. The reason forthis is that the content of the component (a) is low and thereby theperformance inherent to the epoxy resin cannot be sufficiently achieved.

As shown in Table 1, Sample No. 18 is poor in hardness, adhesionproperty, and film formability and is insufficient in hardness, likeSample No. 16. The reason for this is that the number of monofunctionalgroups is increased because of the large content of the component (b),and thereby the performance inherent to the epoxy resin cannot besufficiently achieved.

As can be easily understood from the above results obtained by theexperiments, the resin composition (that is, the fluorine-containingepoxy resin composition) of the present invention is able to form on asubstrate a high quality liquid repellent film excellent in surfaceproperties (hardness and smoothness) and sufficient in liquid repellentproperty and adhesion property. In addition, as for the substrate,although the Si wafer is used as the substrate in the above experiments,it was recognized through experiments that the resin composition of thepresent invention was able to form the above high quality liquidrepellent film on a different substrate such as a resin substrate or ametal substrate. The resin composition of the present invention exhibitsa significant effect, particularly when used for production of an inkjet head. That is, it enables formation of a liquid repellent resinexcellent in surface properties (hardness and smoothness) and sufficientin liquid repellent property and adhesion property on a dischargingoutlet surface of an ink jet head in a desired shape.

For example, when the fluorine-containing epoxy resin composition ineach of Sample Nos. 1 to 8 and 17 according to the present invention isused as a liquid repellent agent in the process described in EuropeanPatent Laid-open No. 631869 for imparting a liquid repellent functionlocally to neighborhoods of discharging outlets of a discharging outletsurface of an ink jet head, the resin composition is effective to beeasily decomposed by excimer laser and hence to achieve an excellentpatterning accuracy because it contains a benzene ring having aconjugated double bond that easily absorbs the energy of the excimerlaser. This makes it possible to form a liquid repellent film excellentin surface properties (hardness and smoothness) and sufficient in liquidrepellent property and adhesion property at the neighborhoods of thedischarging outlets on the discharging outlet surface of the ink jethead in a desired fine liquid repellent pattern, and hence to achieve ahigh reliability ink jet head capable of conducting ink discharging at ahigh accuracy.

On the other hand, when the fluorine-containing epoxy resin compositionin each of Sample Nos. 1 to 4, 7, 8 and 17 according to the presentinvention is used as the liquid repellent agent in the process describedin Japanese Patent Laid-open No. 5-124199, the resin composition is ableto form a liquid repellent film having excellent surface properties(hardness and smoothness) and sufficient in liquid repellent propertyand adhesion property at neighborhoods of discharging outlets on adischarging outlet surface of an ink jet head in a desired fine liquidrepellent pattern, and hence to achieve a high reliability ink jet headcapable of conducting ink discharging at a high accuracy.

Hereinafter, the usability of the fluorine-containing epoxy resincomposition according to the present invention will be described withreference to the following examples. In addition, these examples are forillustrative purposes only, and it is to be noted that the presentinvention is not limited thereto.

EXAMPLES 1 AND 2

In these examples, the fluorine-containing epoxy resin composition ofthe present invention is used for the production of an ink jet head inaccordance with the process which has been described with reference toFIGS. 1 to 12.

EXAMPLE 1

There was provided a silicon substrate having electrothermal convertingelements as energy generating elements 2 capable of generating energyfor discharging ink and an ink supply port. Separately, there wasprepared a coating solution by dissolving a copolymer ofmethylisopropenyl ketone and methacrylic acid=85/15 copolymer(copolymerization ratio: 85/15, weight-average molecular weight: about200,000) in cyclohexanone, to prepare a cyclohexanone solution in aconcentration of 18 wt %. The substrate 1 was spin-coated with theresultant cyclohexanone solution at a rotating speed of 700 rpm,followed by drying on a hot plate at 110° C. for 3 minutes, to form aphotosensitive resin layer 4. Successively, using a mask alignerPLA-520FA produced by CANON INC. (using cold mirror CM-290), ionizingradiation was irradiated onto the photosensitive resin layer 3 only at apredetermined portion not contributing to the formation of an inkpathway for 2 minutes through a patterning mask, thereby thepredetermined portion was solubilized. After that, the exposed portion(solubilized portion) of the photosensitive resin layer 4 was elutedusing methylisobutyl ketone, followed by rinsing by xylene, to form anink pathway-forming pattern 4 a. Here, the ink pathway-forming pattern 4a contributes to the formation of an ink pathway which communicates withthe ink supply port 3 and contains the energy generating elements 2therein. Thus, the resist pattern (the ink pathway-forming pattern 4 a)is left on the location where the ink pathway is provided. The thicknessof the resultant ink pathway-forming pattern 4 a after the elution stepwas found to be 11 μm.

Then, a coating solution was prepared by dissolving, in cyclohexanone,100 parts by weight of an epoxy resin “EHPE3150” (trade name, producedby Daicel Chemical Industries, Ltd. ); 20 parts by weight of an epoxyresin “Epikote 1002” (trade name, produced by Yuka Shell Epoxy KabushikiKaisha); 5 parts by weight of a silane coupling agent “A187” (tradename, produced by Nippon Unicar Co., Ltd.); and 2 parts by weight of acationic polymerization initiator “SP170” (trade name, produced by AsahiDenka Kogyo K. K.), to form a cyclohexanone solution in a concentrationof 50 wt %. The resultant cyclohexanone solution was applied by aspinner onto the ink pathway-forming pattern 4 a of the substrate 1 to afilm thickness (after drying) of 12 μm, followed by drying on a hotplate at 90° C. for 5 minutes, thereby forming a 12 μm coating resinlayer 6 so as to cover the ink pathway-forming pattern 4 a. In addition,the resin composition of the coating resin layer 6 has a negative typephotosensitive characteristic (a portion irradiated with light ishardened). Then, using a mask aligner MPA600 produced by CANON INC., thecoating resin layer 6 was subjected to exposure through a patterningmask shown in FIG. 6 at an exposure amount of 3J/cm². In addition, theprincipal emission line of the MPA600 is present in a wavelength rangemore than 366 nm, and thereby the photosensitive resin layer as the inkpathway-forming pattern 4 a is not substantially decomposed. The coatingresin layer is then heated at 90° C. for 5 minutes, followed by elutionof a non-exposed portion of the coating resin layer using methylisobutylketone, to form discharging outlets.

Next, there was prepared a coating solution by dissolving, inmethylisobutyl ketone, 34 parts by weight of an alicyclic type epoxyresin “EHPE-3158” (trade name, produced by Daicel Chemical Industries,Ltd.) as the component (a); 16 parts by weight of 3-(2-perfluorohexyl)ethoxy-1,2-epoxypropane “MF-120” (trade name, produced by TOHKEM PRODUCTCORPORATION) as the component (b); 25 weight by weight of 2,2-bis[p-(2,3-epoxypropoxy) phenyl]-1,1,1,3,3,3-hexafluoropropane “CHEMINOXAFEP” (trade name, produced by Nippon Mektron, Ltd.) and 25 parts byweight of 1,4-bis (hexaflouro-2-hydoxyl-2-propyl) benzene “1,4-HFAB”(trade name, produced by Central Glass Co., Ltd.) as the component (c);and 1.5 parts by weight of a photo-polymerizing initiator “SP-170”(trade name, produced Asahi Denka Kogyo K. K.) as the component (d), toprepare a methylisobutyl ketone solution in a concentration of 50 wt %.The methylisobutyl ketone solution was further added with 4 parts byweight of the silane coupling agent “A187” (trade name, produced byNippon Unicar Co., Ltd.) and 0.6 part by weight of a leveling agent“EF-802” (trade name, produced by TOHKEM PRODUCT CORPORATION). Thecoating resin layer 6 of the substrate 1 was then spin-coated with theresultant solution at a rotational speed of 600 rpm, and was heated at80° C. for 15 minutes in an oven. Thus, a liquid repellent resincomposition layer (hereinafter, referred to simply as a liquid repellentlayer) 10 having a thickness of 2.3 μm was formed on the coating resinlayer 6 as shown in FIG. 8.

Then, as shown in FIG. 9, the liquid repellent layer 10 was subjected toexposure through a patterning mask 11 having such a pattern as to allowactive energy radiation to be transmitted only through neighborhoods ofdischarging outlets. In this case, the exposure was conducted at anexposure amount of 4J/cm² using the mask aligner MPA600 produced byCANON INC. Thus, the exposed portion of the liquid repellent layer 10was hardened, so that the patterning for the portion other than theneighborhoods of the discharging outlets was conducted in a desiredstate. Then, after heating at 90° C. for 45 minutes in the oven, thenon-exposed portion of the liquid repellent layer 10 was eluted usingmethylisobutyl ketone, to locally form a liquid repellent pattern 10 aonly on the neighborhoods of the discharging outlets as shown in FIG.10. The local liquid repellent pattern 10 a not perfectly hardened wasfurther heated at 100° C. for one hour for the purpose of preventing thepattern from being deformed in a step of eluting the solid layer whichwill be described later.

Next, in order to decompose the ink pathway-forming pattern 4 a, asshown in FIG. 11, ionizing radiation was irradiated onto the inkpathway-forming pattern 4 a through the liquid repellent pattern 10 aand the coating resin layer 6 for 2 minutes using a mask aligner PLA-520produced by CANON INC. (cold-mirror CM290)

The substrate 1 was then immersed in methylisobutyl ketone for 15seconds while effecting ultrasonic wave thereinto, to elute the inkpathway-forming pattern 4 a. At this step, since the ink pathway-formingpattern 4 a was already decomposed, it could be easily eluted. Inaddition, although the copolymer used for the coating resin layer 6 isof an ionizing radiation decomposable type, in the case of using CM290,the decomposition reaction is substantially negligible. In this way, anink pathway 8 was formed, and an ink jet head shown in FIG. 12 wasobtained.

EXAMPLE 2

In this example, an ink jet head was prepared in the same manner as thatof Example 1, except that 20 parts by weight of the 2,2-bis[p-(2,3-epoxypropoxy) phenyl]-1,1,1,3,3,3-hexafluoropropane “CHEMINOXAFEp” (trade name, produced by Nippon Mektron, Ltd.) and 30 parts byweight of flourohexanediol were used as the component (c) of the resincomposition for forming the liquid repellent layer 10.

EVALUATION

Each of the ink jet heads prepared in Examples 1 and 2 was examined interms of printing performance in the following manner. That is, the inkjet head was mounted on an ink jet system shown in FIG. 13, and wassubjected to test printing using the black ink for BJC4000 produced byCanon for 30 pieces of A4 sized sheets. As a result, it was revealedthat each of the ink jet heads prepared in Examples 1 and 2 was able toconduct stable printing with a high accuracy.

EXAMPLE 3

In this example, the fluorine-containing epoxy resin composition of thepresent invention was used as a paint for a hull.

First, there was prepared a resin composition containing 60 parts byweight of a bisphenol A type epoxy resin “Epikote 828” (trade name,produced by Yuka Shell Epoxy Kabushiki Kaisha) as the component (a); 10parts by weight of the 3-(2-perfluorohexyl) ethoxy-1,2-epoxypropane“MF-120” (trade name, produced by TOHKEM PRODUCTS CORPORATION) as thecomponent (b); and 30 parts by weight of 1,3-bis (glycidoxypropyl)tetramethyldisiloxane “LS7979” (trade name, produced by Shin-EtsuChemical Co., Ltd.) as the component (c), wherein the components (a),(b) and (c) were uniformly mixed in a compatible state. The resincomposition was further added with 60 parts by weight of asiloxane-bonded amine hardening agent “TSL9346” (trade name, produced byToshiba Silicone Co., Ltd.) and 3 parts by weight of the silane couplingagent “A-187” (trade name, produced by Nippon Unicar Co., Ltd.), anduniformly mixed therewith into a compatible state. The resultant resincomposition is further added with 10 parts by weight of titanium oxideas a coloring agent dispersed therein, to prepare a paint.

The paint thus obtained was applied on a portion of a hull to be paintedusing a brush, followed by being left at room temperature for 24 hours,and was hardened using an infrared ray lamp. The hull thus painted,which was sunk in the sea for 20 days and drawn up, was examined insurface state. As a result, it was observed that the painted portion waskept in a desired state, that is, the sticking of acorn shells, moss,and seaweeds on the painted portion of the hull was significantlyreduced.

EXAMPLE 4

In this example, the fluorine-containing epoxy resin composition of thepresent invention was used for bonding of a lid of an alumite madekettle with a wooden handle.

First, there was prepared a resin composition containing 60 parts byweight of the bisphenol A type epoxy resin “Epikote 828” (trade name,produced by Yuka Shell Epoxy Kabushiki Kaisha) as the component (a); 10parts by weight of the 3-(2-perfluorohexyl) ethoxy-1,2-epoxypropane“MF-120” (trade name, produced by TOHKEM PRODUCTS CORPORATION) as thecomponent (b); and 30 parts by weight of 1,3-bis (glycidoxypropyl)tetramethyldisiloxane “LS7979” (trade name, produced by Shin-EtsuChemical Co., Ltd.) as the component (c), wherein the components (a),(b) and (c) were uniformly mixed with each other in a compatible state.The resin composition was further added with 30 parts by weight of asiloxane-bonded amine hardening agent “LS7430” (trade name, produced byToshiba Silicone Co., Ltd.) and 3 parts by weight of the silane couplingagent “A-187” (trade name, produced by Nippon Unicar Co., Ltd.), toprepare an additive. In this adhesive, the siloxane-bonded aminehardening agent and the silane coupling agent were uniformly mixed withthe resin composition into a preferable compatible state.

The adhesive thus obtained was applied using a brush to the handle at aportion to be bonded with the lid of the kettle, and the handle wasbrought in close-contact with the lid. The handle and the lid in such astate were left at room temperature for 24 hours, followed by thermalcuring at 80° C. for 2 hours for hardening the adhesive, to thuscomplete the bonding of the handle with lid. The kettle covered with thelid bonded with the handle by means of the adhesive was used for boilingwater five times, which gave a preferable result that the handle and thelid were not separated from each other.

TABLE 1 Sample No. 1 2 3 4 5 6 7 8 9 10 Component EHPE-3158 34 34 34 34(a) Epikote 828 50 40 CY179 55 70 Component MF-120 20 16 10 16 16 16 20100 (b) MF-130 16 Component CHIMINOX AFEp 20 25 25 20 20 100 (c)1,4-HFAB 21 25 25 25 LS7970 30 25 20 fluorohexanediol 30 ComponentSP-170 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 (d) Cu(CF₃SO₃)₂ 1 1 DEFENSA7710CTX-805A CHEMINOX FAAC Sefral Coat A-101B Evaluated Hardness Test ⊚ ⊚ ⊚⊚ ⊚ ⊚ ⊚ ⊚ Δ — Item Liquid Repellent ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ × — PropertyAdhesion ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ × — Property Film Formability ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ×— Solvent- ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ Suitability Total Evaluation ⊚ ⊚ ⊚ ⊚ ⊚ ⊚⊚ ⊚ × × Sample No. 11 12 13 14 15 16 17 18 19 20 Component EHPE-3158 8434 5 15 34 (a) Epikote 828 50 CY179 44 Component MF-120 20 16 5 16 16 46(b) MF-130 Component CHIMINOX AFEp 31 54 44 25 (c) 1,4-HFAB 30 25 25 25LS7970 80 10 30 fluorohexanediol Component SP-170 1.5 1.5 1.5 1.5 1.51.5 1.5 1.5 (d) Cu(CF₃SO₃)₂ DEFENSA 7710 100 CTX-805A 100 CHEMINOX FAAC16 Sefral Coat A-101B 20 Evaluated Hardness Test — — Δ Δ ⊚ Δ ◯ Δ — —Item Liquid Repellent — — ⊚ ⊚ × ◯ ◯ ◯ — — Property Adhesion — — Δ Δ ◯ ×◯ × — — Property Film Formability — — ⊚ ⊚ ◯ × ◯ × — — Solvent- ◯ ◯ ×*1×*1 ◯ ◯ ◯ ◯ ◯ ×*1 Suitability Total Evaluation × × Δ*2 Δ*2 × × ◯ × × ×*1: selectively soluble only in specified solvent (freon base solvent)*2: since solvent-suitability is evaluated at (×) but is soluble inspecified solvent (freon based solvent), total evaluation is evaluatedat (Δ)

What is claimed is:
 1. A fluorine-containing epoxy resin composition fora discharge outlet surface of an ink jet head, said compositioncomprising: a component (a) in an amount of from 5 to 80 parts byweight; a component (b) in an amount of from 5 to 40 parts by weight;and a component (c) in an amount of from 5 to 80 parts by weight,wherein said component (a) comprises a polyfunctional epoxy resin havingtwo or more epoxy groups in one molecule and not containing F and Si;said component (b) comprises an epoxy compound having a perfluoro groupat a terminal; and said component (c) comprises a compound having two ormore epoxy groups in one molecule and containing F or Si, and a compoundhaving two or more of one kind or two or more kinds selected from analcohol group, a carboxylic acid group, and an amine group, andcontaining F or Si.
 2. A fluorine-containing epoxy resin compositionaccording to claim 1, further containing a polymerizing catalyst.
 3. Afluorine-containing epoxy resin composition according to claim 2,wherein said polymerizing catalyst is a thermal-polymerizing catalyst.4. A fluorine-containing epoxy resin composition according to claim 2,wherein said polymerizing catalyst is a photo-polymerizing catalyst. 5.A fluorine-containing epoxy resin composition according to claim 1,further containing a hardening agent.
 6. A fluorine-containing epoxyresin composition according to claim 5, wherein said hardening agent isan amino compound containing a siloxane group or perfluoro group or anacid anhydride of said amino compound.
 7. A fluorine-containing epoxyresin composition according to claim 1, further containing a silanecoupling agent.
 8. A fluorine-containing epoxy resin compositionaccording to claim 1, further containing a coloring agent.
 9. Afluorine-containing epoxy resin composition according to claim 1,wherein said resin composition is in a solid state at normaltemperature.
 10. A fluorine-containing epoxy resin composition accordingto claim 1, wherein said composition is in a liquid state at normaltemperature.
 11. A fluorine-containing epoxy resin composition accordingto claim 1, wherein the weight mixing ratio between said compoundcontained in said component (c) which has two or more epoxy groups inone molecule and contains F or Si, and said compound contained in saidcomponent (c) which has two or more of one kind or two or more kindsselected from an alcohol group, a carboxylic acid group, and an aminegroup and contains F or Si, is in a range of from 1:5 to 5:1.
 12. Aprocess for conducting surface treatment for a discharge outlet surfaceof an ink jet head by forming a liquid repellent film thereon,comprising: (1) a step of coating said discharge outlet surface of saidink jet head with a fluorine-containing epoxy resin composition, saidfluorine-containing epoxy resin composition comprising: a component (a)in an amount of from 5 to 80 parts by weight; a component (b) in anamount of from 5 to 40 parts by weight; and a component (c) in an amountof from 5 to 80 parts by weight, wherein said component (a) comprises apolyfunctional epoxy resin having two or more epoxy groups in onemolecule and not containing F and Si; said component (b) comprises anepoxy compound having a perfluoro group at a terminal; and saidcomponent (c) comprises a compound having two or more epoxy groups inone molecule and containing F or Si, and a compound having two or moreof one kind or two or more kinds selected from an alcohol group, acarboxylic acid group, and an amine group, and containing F or Si; and(2) a step of forming a liquid repellent film by hardening saidfluorine-containing resin composition coated on said discharge outletsurface of the ink jet head.
 13. A process according to claim 12,wherein said fluorine-containing epoxy resin composition furthercontains a polymerizing catalyst.
 14. A process according to claim 13,wherein said polymerizing catalyst is a thermal-polymerizing catalyst.15. A process according to claim 13, wherein said polymerizing catalystis a photo-polymerizing catalyst.
 16. A process according to claim 12,wherein said fluorine-containing epoxy resin composition furthercontains a hardening agent.
 17. A process according to claim 16, whereinsaid hardening agent is an amino compound containing a siloxane group orperfluoro group or an acid anhydride of said amino compound.
 18. Aprocess according to claim 12, wherein said fluorine-containing epoxyresin composition further contains a silane coupling agent.
 19. Aprocess according to claim 12, wherein said fluorine-containing epoxyresin composition further contains a coloring agent.
 20. A processaccording to claim 12, wherein said fluorine-containing epoxy resincomposition is in a solid state at normal temperature.
 21. A processaccording to claim 12, wherein said fluorine-containing epoxy resincomposition is in a liquid state at normal temperature.
 22. A processaccording to claim 12, wherein the weight mixing ratio between saidcompound contained in said component (c) which has two or more epoxygroups in one molecule and contains F or Si, and said compound containedin said component (c) which has two or more of one kind or two or morekinds selected from an alcohol group, a carboxylic acid group, and anamine group and contains F or Si, is in a range of from 1:5 to 5:1. 23.A process according to claim 12, wherein said liquid repellent film isselectively formed at a specified region on said discharge outletsurface of the ink jet head.
 24. A process according to claim 23,wherein the selective formation of said liquid repellent film isconducted by patterning said resin composition by a photolithographyprocess.